Process for manufacturing aluminum compounds



Mar. 3, 1925. 1,528,039

E. R. WOLCOTT PROCESS FOR MANUFACTURING ALUMINUM COMPOUNDS Filed April 14', 1920 2 2 15 cnn" Hydrocerbw Fe@i ACQ Clay Sarl' Cal Fq'g ATTORNEY v Patented Mar. 3,. i925.

1,528,039 *lia'rl'alsrrA OFFICE.

EDSON B. WOLCOTT,. 0F^LOS .ANGLES CALIFORNIA, ASSIGNOR, BY MESNE ASSIGN- MENTS, To Tim. 'rnxas- COMPANY o TEXAS.

rnocnss ron IaNUmcTUm-Ne ALUMINUM comoms.'

Appuaaoii ma Aprn 14 pounds, fromclayq bauxite, shale, or other l material containing silicate of aluminum, or oxygen' containing aluminum compounds, with or without other constituents.

An important object of the present invention is to provide. for treatment of clay, shale, etc., which does not naturally conthin carbonaceous' material .in. sutlicien't quantity to furnish the carbon required for the decomposition of the silicate, or Athe conversion of the silicate -OLthegform of'chloride, or other desiredsalt.

' My invention provides for thel utilization of such silicates byadding thereto carbo- 1920. serial No. s715778.

lized in any suitable manner, for example, in the dye industry, or in' petroleum retin-ing, or itmay be subjected to further treatment for the production of aluminum therefrom in well known manner.

Another object of'my invention is to provide for recovery lof the fume land gaseous constitutents passing from the retort includ-- ing chlorine and combustible gases, particularly carbon monoxide.

A further object of thev invention is to provide for cyclic operation of the rocess in such manner as to effect rapid pro uction of aluminum chloride by the use of excess .chlorine in the retoting operation andto provide for recovery and re-use of the excess chlorine so as t-o carryout the process in the most economical manner.

Another object ofthe invention is 'to provide for carrying out the process in such manner as to dispense as far as possible with the use of any fuel otherthanwhat is produced by the operation of the process itself. For this purpose my invention pronaceous material capable of producing on vides for recoverv and use as fuel of hydrodestructive distillation suiicient hydrocarbon to furnish .all-, or aconsiderable portion of thefuel required'. for Vcarrying on the process'and suiicienf' residual carbon` to effect in the presence fof chlorine the A production of aluminum chloride from'the aluminum silicate content of the material. This carbonabeous material may consist, fo example, --;of coal, asphaltic material or lowgrade f.petroleum. The mixture of.

carbonaceou's material and oxygen-con-v taining aluminum compound is subjected to a preliminiiidistillation to drive' oi the volatile constituents, or 'hydrocarbons contained i bonaceo'us ofA carbon ,mixed with the s'ili'cious mate-fi` rial, in suitable 'condition for production of aluminum chloride, or other salt:'thferefronyA by a chloridiziiig'fvolatilizatiol "operation yor simila-r-operation.- .1 .My invention is intended partcula y'ffogrthe production of aluminum chloridegor other halide, either purey orf mixed with other chlorides, or of va.4v double chloride-of aluminum and other metals, for example, of sodium and aluminum and the chloride or halide salt thusproduced may. be utiproduced in carrying out the'l heating operation in such retort.-

vIn the accompanying drawings, Fig. 1

illustrates diagrammatically an .apparatus suitable for carrying-out-my invention, this figure illustrating vthe v use of chlorine as a.

chloridizing agent.'

Fig. 2 isa iow sheetof an embodiment -of the invention off the process in which sodium chloride is used as a chloridizing agent.

fof this invention." The respective bins 1 and 4 for feeding the silicious material to suitable crushing or grinding means, indi' mixedfmaterial being delivered-throughput The apparatus shown in Fig. 1 comprises teria-1,. vleaving 'thel residuia bin 1 forl storage anddelivery,.for ex.'

f""ample,"'of th e V clay or argillaceous matej 'in2 for storage and delive aw-du'st; "brea', orother material sufficiently igh in carbon content to serve the purpose l and 2 are provided with yfeeding means '3 ion letl 8 to suitable storage means, here indicated as a charging floor from which the retort hereinafter described may be charged, either by hand orautomatically by suitable means in the usual manner of coke or' gas retorts.V

A retort, indicated at 11, is mounted in a combustion chamber, or furnace 12, which is heated by a burner 13 so as to Iheat the contents of the retort 11 to the required high ten'lperature, said furnace having an outlet stack, indicated at 15. The retort 1l is provided with a charging door 14 which may be opened or removed to permit charging of the rctorts with the material to be treated and said retort is further provided with an outlet pipe 16 through which thegas and fume produced in the retort may pass to suitable means for treatment further as hereinfater described.

In the form shown in the drawings, the retort is of the horizontal type and is made of silica, or other suitable material, so as to withstand the high temperature and the ac-t tion of the chemical agents. Suitable means, such as inlet 'pipe 17 is provided for supplying the chloridizing agent, for example, chlorine, to the interior of the retort 11, such agent being drawn from a'pipe 18 provided with a valve 18'; another pipe 19 provided with' a valve 19' may connect with the pipe 17 to deliver hydrochloric arid gas thereto, as hereinatfter described.

The outlet pipe 16 leads to sui-table means for separating and recovering the several constituents of the gases and fumes passing off from the retort 11. Such means` may comprise several recovery devices 20, 2l and 22, connected to the outlet pipe lthrough valves 23, 24 and 25, so that said recovery devices may be brought into operation successively or alternatively. The device 20 consists of' a condenser having suitable means 27 for circulating cooling medium therethrough to cool the gases delivered from the outlet pipe 16 and the corresponding valve 23 being operi during the first stage of the operation so that the hydrocarbons produced in such first stage are partly condensed in the device 20 and pass ofi' through an outlet 28, theresidual or'uncondensed gases being forced by piunp 29 to a receiver`30 from whichthe pipe 31leads-to a burner 32 acting as an auxiliary burner to the burner 13 aforesaid.

The device 21 is' for the purpose of removing the ferricchloride produced in a second stage of distillation and is provided with a Vmeans 33 for circulating cooling medium in of the distilling'o eration. This device is illustrated as an e ectrical,"preciptator but it is understood that any-suitable collection means may be used for this purpose.

The device 22 is provided with an outlet l37 for the condensed aluminum chloride and with an outlet 36 for conducting the residual gases .to a washing tower or spray chamber 38 adapted for collection or removal `oi chlorine and hydrochloric arid gases. This device 38 isprovided with means, indicated at 40, for supply of lime-water, or equivalent thereof, and with an outlet 41 through which the reaction product is discharged to a -tank or Sump 43. I prefer to provide in this connection means or convertingr the etfluent gases Jfrom the spray chamber 25% to the form of'calcium chloride, or equirelent material, for example, by supplyingr hydrochloric acid to this tank through a pipe 14- and the calcium chloride solution produced may be forced by pump 45 to a pipel 46 leadT ing to the mixer 7 abov ,described so as io mix the calcium chloriulsolution with the' mixture of argillac'eous nuiterial and carbonaceous material. The ellluent gases from the spray cham-ber 38 may be forced by pump 48 to a burner 49 acting as an auxiliary burner in heating the chamber or furnace 12.

Myprocess may be carried out in the above described apparatus as follows:

Clay, shale, or other rock, or material containing. aluminum silicate, or other oxyl gen-containing aluminum compound. such as bauxite, or corundum, is supplied from the bin 1 to a Crusher or grinder 5 and the finely ground material is mixed in the mixer 7 with suitably ground coal, brea, saw-dust, or other carbonaceous material.`

The resulting 4mixture' of inely divided oxygen-bearing aluminum `compound andv carbonaceous material is charged in the rctort 11. either by hand or by the operation of suitable mechanical means. and said retort is then heremeticaly closed at the charging door 14 and is subjected to heat produced in the combustion chamber 12... In the case of shale, or argillaceous material containing an appreciablel amount of iron compounds, I prefer to carry out the distillation of the material in three stages.

In the first stage,Y the heat applied to the retort 11 is such as to subject the, carbonaceous material in the'mixture to destructive distillation to drive ofl" hydro-carbon compounds and other organic compounds. which pass out through the pipe 16 and are conducted to the condenser 20, valve 23 being opened and the valves 24 and 25 being closed at this time. ',Any water contained in the mixture will also be driven off in-this operation, either before or during the volatilization of the hydrocarbons, and may be collected, together with or separately from -favorable condition forv reaction therewit in promoting the -formation of aluminum", chloride -in the lastl stage of distillation but"- also serves to holdf the massfopenl or in porous condition, facilitating the accessoi- 'vas to f passes lperature as to cause condensation and pr cipitation of theialuminum chloride. --If desired, a cooler or condenser may be used in advance ofthe electrical precipitator to enfsure condensation'of the aluminum chloride as 'fume preparator to the precipitation of 4 blev chloride of 'sodiuml and aluminum is 125 The collected aluminumv c produced, which'is collectd and drawn voif .in an suitable manner through I 4 i the voutlet 37 .an the residual gases 'contain- '-'-ingv= f more or lesscarbon monoxide and the freechlorineare passed through the spray`v the hydrocarbons. Condensed hydrocarbons may pass out'through the outlet 28 to suitf able storage means and the residual gases are pumped by the pump 29,y fto"receiver 30 and delivered as fuel tof the combustion chamber 12 through burner 32. If desired, all the'hydrocarbon'sor organic compounds 4.passing from the retort in this operation' maybe delivered directly to the burner 32 for combustion` as fuel. The carbon-aceous v material havingbeen substantially freed of volatile matter, including hydrocarbons and water, in'this first stage ofdistillation, the valve 23 is then closed and valve 24'is opened and hydrochloric acid gas, preferably With-5a trace of chlorine passed in the retort 11, for

example, through pipes 19 and 17, the heat of the retort being maintained at such a degree as toocause reaction between the hydrochloric acid and the iron compounds present, resulting in the productionl of fer'j ric chloride, or a double chloride of iron and aluminum, which ,passes oil through the pi'pe'lv and is collected -in the condenser 21, or is otherwise' Ydisposed of. This -second stage of distillation results in the production in the retort of a substantially pure oxygen-containing compound of aluminum g 36 intimately mixed With residual carbon resulting fromv the destructive distillation of the vcarbonaceous material. This carbon so distributed throughout the mass'of oxygen-v bearing aluminum compound is not only in the` chloridizing agent thereto.

admitted -to the retort 11, for example,

lthrough pipes 18 and 17, andtheheatofthe l'retortis maintained at such degree vto produce a reaction between ythe oxygen-v containing aluminum compound andv the chlorine, together withthe carbon present so@l 'p i tain's considerable iron.

My-inven'tion may also lbe' applied in vconnectionwith the use of other chloridizing separaterecovery means 22 this recovery' means consisting, for example, of an el trical rprecipitator maintained at such te said fume in the e ectrical precipitator.,`

loride mayv be produce aluminum chloride which v'anys'uitable manner,'y .Qlectrolyticl production meta lic alumi- .1,cagent, producing calcium hypochlorite,

which flows into theA tank 43' and which may be cbnverted into calcium chloride, or equivalent chloride or halide, by the addition of h` drochloricy acid, or other halogen compoun added thereto through the supply-means 44, the 'resulting calcium chloride or halide, being,'if desired, umped back to the. mixer 7 .for mixing wit the supply of finely divided silicate material and carbonaceous'niaterial. Calcium chloride added in this manner to the mixture acts similarly to chlorine in eife'cting chloridization and volatilization-offaluminum chloride, and by returning thecalciu-m chloride to the cycle of operat1ons,i asstated, I am enabled to correspondinglj reduce the amount Qf chlorine reagent. -alcium chloride, magnesium chloride, orsimilar halide,may also be addedfto `the mixture in the rst 'place in such quantitity vas to more or .less completely hv, the use of free chlorine. The residual; ,sesitfrom the spray tower 38 consist largev Vfof-carbon monoxide, which may be utilize 'i'n any suitable manner, for-example, by 'forcing same by pump 48 to burn'erg49 -for the combustion chamber 12.

,Sil

A nyree" chlorine produced in the 0 9'. ,I

eration lof lapparatus 13 (Fig. 1) may e V returned to the retort 11, or otherwise utilized.v "l l ,.In the treatment' of' aluminum silicate rocks, 'or clays, which are substantiallyfree' *100 om iron, the second stage ,ofl distillation above described for the removal of ferrie chloride may be dispensed with.

In ca se the anhydrous aluminum chloridel i.producedby my process is used in, petroleum refining, or for similar organic reactions, the urese'nce of anhydrousferric vchloride is 'notiuobjectionabla and the second stage of d tillation for thejseparate removal of y, therefore, be omitted, even when 110 ldized aluminum compound used conor.' halidizing agents, jforjex'ample, as indi- 11W' opted-by the flow sheetin-Fig. 2,4 "salti may beadded directly to the lmixture of clay, "other aluminum silicatev\li1ateria`lf, and coa1,:`o`r other carbonaceous materialthese and; then intermixed and passed to the 1re-4 `tort 11, thefop'eration thenproceeding' as indicated by theilow sheet inthe samemanner as -above described,f except that a dou-v utilized in fol'fxam le, in the num..l ,Y

In place-oichlorie; chloride,

threecostituentsbeingeach iinelyground other halogens, or a halide, may be used, for example, bromine, sodium bro'mide, caleium chloride, magnesium chloride, calcium ffuoride, etc. VVhere an alkaline earth chloride. such as calciumr chloride, is used, the reaction results in production' ofcalcium silicate in'the residue, and volatilization of .aluminum chloride. The function of the carbon in the reacting mixture is, in this case, mainly to maintain 'a non-oxidizing atmosphere', so as to prevent decomposition of the aluminum chloride formed. In case sodium chloride is used as a chloridizing agent, a somewhat similaireaction may take place. sodium silicate being formed and a double chloride of sodium and aluminum being volatilizcd, so that in this case also the function of the carbon is mainly to maintain a non-oxidizing atmosphere. ln case free chlorine is used as the ehloridizing agent, the carbon acts as a reducing agent for the aluminum compound as Well as 'preventing decomposition of the aluminum chloride formed. ln anycase the carbon present .also acts as a means for maintaining the porosityy of the mixture.

My invention may also be carried out in such manner as to dispense with the preliminary distillation of hydrocarbons, in case the amount of such hydrocarbons prescnt is not suflicient to Warrant recovery thereof. For example, finely divided coke may be intimately mixed with the clay or aluminum silicate material and the mixture subjected to heat in the presence of a chloridizim.y or halidizing agent. as above described, except that the first stage of distillation above described is omitted or is employed only to drive ofl Water from the mixture. ln thi5`case, the separation of iron as' ferrie chloride and the condensation and collection of aluminum chloride, or 'other aluminum compound, may take place in the same manner as above described, and the residual gasesv may be treated as described for the separation and recoveryof chlorine in the form of an alkaline earth chloride which is returned to the mixture for distillation, and'in case the gases remaining after separation of the chlorine have a fuel value, they may be burned to produce heat for thev distilling operation. The utilization of the residual gases as fuel for the distilling operation is of especial importance when free chlorine is used as a chloridizing agent, as the reaction then involves the production of an 'amount of carbon monoxide gas corresponding tol the amount of aluminum chloride produced. For the purpose of` accelerating the reaction and in order to ensure the production of carbon u'apnoxidein the -gases passing 'from theretort with a minimum amount of carbon dioxide, it is preferred to carry out the distillng operation for the productionqgff aluminum chloride froml the' mixture' of aluminum silicate material and carbon in the presence of a chloridizing agent, at a temperature of 1000o C., or` over.

ln order to utilize the carbon monoxide and chlorine, the gases passing from the 'distilling operation may, after removal of the aluminum chloride, be conducted to a second retort containing a mixture of aluminum silicate material and oxygen-bearing aluminum compound, and maintained at Such temperature .by external hea-ting, if necessary, to provide for reaction between the said material and the said carbon monoxide. and a chloridizing` agent, which is caused to be present, either as chlorine carried forward with the carbon monoxide from the first retort, or addedto the second retort, either as free or combined chlorine. Aluminum chloride is thereby produced, which 'fumes off in the second retort, t0-

gether with the gases resulting from the reaction, and is then condensed and collected, as above described. This operation may be carried on in an apparatus similar to that shown in Fig. 1 with the addition of another retort similar to retort 11 for receiving' the carbon monoxide and chlorine resulting from the operation of the first retort` or, if desired, a mixture of carbon monoxide and .chlorine passing, for example, from the precipitator 22 may be drawn through pipe 51 to a pump 52 and delivered back to the same retort 11,01'. one of the same bench or set of retorts.' lIn this case the Acarbon monoxide resulting from the operation labove described in retort 11 is returned and acts -with the retorting of naturally occurring mixtures of argillaf'eous and carbonaceous materlals, such as 011 shales, or low grade coals. In this respect, my invent-ion in-j oludes the -process consisting 1n reducing such naturally occurring mixtures to a suitable divided condition, heating such mixtures in a retort in the presence of a'chlo,

ridizinglagent in such manner as to produce aluminum -chloride and a mixture of carbon monoxide and chlorine gas, and utiliz'- ing such carbon monoxide by oxidation thereof, either by way of combustion in the retorting furnace, or as a reducing a nt in the retort itself. While, therefore, t e formation'of an artificial mixture of oxygencontaining aluminum compound and carbonaceous material is of value where a naturally `occurr1ng mixture is not avaliable, my

invention is not limited to the use of such artificial mixtures y as far as regards the other features` of the process, but includes the use'of any mixture, whether natural or artificial, containing oxygen-bearing aluminum.compound and carbonaceous material `in. proper proportions'-thel process being so sirable to' subject the mixture of carbon` monoxide an chlorine gases to a suitable catalytic agent, such as light, or tinely divided carbon, to produce phosgene gas, which is then conducted to\the retort 11, or to a similar retort, maintained at suitable temperature to cause reaction between the phosgene gas and the oxidized aluminum compound present to produce alum1num chloride. In this case, as well as in the case where the carbon monoxide and chlorine are used d1rectly 1n a retort containmg oxidized aluminum compound, the amount of carbon present with such compound may be reduced to a minlmum, the reducing action being'ef- 'fected by carbon monoxide. yIt will be understood that the effluent gases from this secondary distilling operation using carbon monoxide as thereducing agent will contain carbon dioxide in a'large proportion andv will generally be discarded after separation of the aluminum chloride therefrom.

Instead of using free chlorine in carrying out my process, I may use an alkaline earth f chloride, such as calcium chloride, or magnesium chloride, such chloride ,reactingI wi-th .the mixture (either artificial or natural) of oxygen-containing aluminum compound and carbonaceous material to form aluminumchloride, the calcium content remaining in the residue, and the aluminum chloride being volatilize'dsand collected as above described. The calcium chloride so used may be, in part at least, produced in the treatment of the ases and vapors passing from the retort, as a ve described. That partei my invention which relates to the recovery ofthe halogen from the' residual gases by treatment of same by suitable re ents to form a halide, and returning such alid to the retorting operation, is also applicable in connection with theretorting ofl a natural mixture (such as oil-shale, or slaty coal) of oxygencontaining aluminum compound and carbonaceous material, as well as to-an artiicial mixture of oxygen-bearing aluminum com poundand carbonaceous material (such 'as coal, brea, peat, coke,'etc).

The phosgene gas produced, as above described, by treatment of thev mixture of carbon monoxide and chlorine may be utilized for other purposes, or disposed of as a commercial product, if desired. Y

In making a mixture of oxygen-bearing aluminum compound and carbonaceous ma' teria-l for use in. the process above described,

I may utilize as the said carbona'ceous matcrial the residue of oil reining. operations 1n wlnch aluminum chloride has been used as a reagent.-V Such resldues contain alumlnum compound with carbonaceous material and maybe mixed wlth a suitable additlonal quantityl of oxygen-containing aluminum compound and then retorted in the presence of free chlorine, or otherchloridizing agent, as above described, for the production ofl aluminum chloride, or other compounds of aluminum.

`What I claim is:

1. The process which 'consists in subjecting a mixture of aluminum silicate material" and carbonaceous material to heat to effect destructive distillation of the carbonace'ous material, collecting the products so distilled,

subjecting the residual mixture oi aluminum v silicate material and' residual carbon to further' heating-action in the presence of a A halidizing agent to roduce and volatilize a halide compound o aluminum, se arating such compound from the gases an passing ofi' therewith in they volatilization operation, and treating the residual gases with-'materialc'apable of absorbing the halogen in such gases andvapors to -form a halide and returning the halide so formed to the vapors heating and volatilization stage of the cycle of operations.

2. :The process'which consists -in subjecting a mixture of aluminum silicate material and vcarbona'ceous material to heat to effect destructive distillation of the carbonaceous material, collecting the products so distilled,

vsubjecting the residual mix-ture of aluminum silicate material and residual carbon "to .treating the residual gases with material cai pable of absorbing the. chlorine in such gases and vapors to form a chloride and returmn the chloride so formed to the heating anvolatilization stagesof the cycle of opera'-` tions;

3. -The process which consistsin subjectin aluminum silicate material and carbon to eat in the presence of chlorine to produce and drive o aluminum chloride, together with carbon monoxide and chlorine, treating the' gases passin from s uch heating o ration to remove c orme therefrom, an uti-.i24 lizing the chlorine so removed to produce a bringing the'same into contact with heated aluminum silicate material and carbon.

a. The 'process which consists in subjecting a'mixture of aluminum silicate materialand carbonaceous material to heat to effect destructive distillation of the carbonaceous material, collecting the products so distilled, subjecting the residual material to the `further action of heat in theA presence of hydrochloric acid gas to volatilizc and remove from the aluminum silicate material any iron contained therein, subjecting the residual mixture of aluminum silicate and carbon to heat in the presence of a chloridizing age-nt to produce and volatilize a chlorine compound of aluminum, and collecting such compound.'

5. The, process which consists in subjecting a mixture of' oxygen-containing aluminum compound and carbon to heat in the presence of an excess of chlorine to produce l and volatilizc aluminum chloride, separating the aluminum chloride from the gases and vapors produced in the distiliing operation, passing the remaining gases and vapors containing chlorine through lime Water whereby calcium hypochlorite is formed,

treating said hypoclilorite witlra halideto form a halogen compound and bringing said halogen compound in contact With a 'mixture of oxygen-containing .aluminum compound and carbon heated in the 'of a chloridizing agent.

' (3. The process which consists in subjecting materiahincluding an oxygen-containpresence v ing compound of aluminum, together with 'aluminum chloride.

carbon, to heat in the presence of a chloridizing agent, to produceand drive off aluminum chloride, subjecting the gases and vapors result-ing from such operation to condensing and collecting-.operations to remove aluminum chloride therefrom, and passing residual gases and'vapors containing residfurther portion of material, 'including L oxygen-containin compound o'faluminuiii,` together with 'car on, in heated condition to utilize said residual chloridizing'agent in the production of a--further quantity .of

A vi920. y vconsists in subjecting material comprising oxygen containing compound of aluminum, togetherfwith carbon, kto heat in aretort in the presence of an excess of chlorine to produce anddrive olf gases containing aluminum chloride and chlorine, separating aluminum chloride from said gases, and recovering chlorine from said gases, and utilizing the chlorine so recovered in cyclic operation of the process. i

S. In the manufacture of aluminum chlorid from bauxite and other forms of alumina with the aid ofchloiin, the piocesswvhicb con'iprises employing in conjunction with the chlorin some ot the Waste gases of the operation itself.

0. In the manufacture of aluminum chlorid vapors from alumina, carbon and chlorin in av suitable reaction chamber, the process which comprises collecting the vapors and gases formed in the reaction, cooling to condense aluminum chlorid and returning a portion of the uncondensed gases to the reaction chamber. v

l0.` In the manufacture of aluminum chlorid from alumina. and chlorin in the presence of a reducing agent, the process which comprises cooling the eiiluent mixture of gases and vapors to condense aluminum chlorid therefrom and returning a portion of the residual gases to the reaction zone to accelerate the reaction of the chlorin upon the alumina.

f ll. In the manufacture of aluminum chlorid, the process that comprises reacting 'alummous material with a chloridizing agent, separating ,the aluminum chlorid :from the evolved vapors and cyclically returning uncondensed constituents to the reininum Vsilicate material With a chloridizing -ag'ent in thepresence of a reducing agent, ual chloridizing agent into contact 'Witha separating from the evolved vapors ,the

f'aluminum chlorid produced and utilizing 'fthe remaining vapors for treating additional quantities of aluminum vsilicate material.

In testimony 'whereof I have hereunto subscribed my name this 5th day of April nnsoN n WoLcoTT. 

